Liquid phase chlorination



Patented June v14, 1949 lPurdue Research Foundation,v West-Lafayette.f

llud., a corporation of Indiana i s n i,implication December 20, 1945; Serial No. 63 L 13 claims. (cl. 20A-1,63)

assi

rination to continue the chlorination'- for a suflciently long period to produce substantially only chlorohydrocarbons having a density above about 1.3 without producing undesired chlorinolysis and w 4This invention relatestora continuousprocess y ion-fthe;chlorination' of aliphatic and alicyclic v hydrocarbons, having inthe .moleculelbetween three-.and eight carbon''ator'ns, inclusive, and

,4 f chlorinated'derivatives thereof, and is particularlyy 5I "chlorinating'excessively -some of the substances concerned with-`V the production*therefromaiof a present. Recyclingwoffa"considerable-amount of Y, .'highly'chlorinatedshydrocarbonmixtures. distilled insufciently chlorinatedt substances is 'j The factthatniosthydrocarbons and'chlorine also necessary and; the .partially chlorinated hyreact inthe f presence ofi-light f with explosive v f drocarbons used as starting material renders the "violencef over :a Wide "rang"i "of 'proportions hasy l0 process uneconomical. This is especially; true in :presented amaj'or dii'cult'yf in processes involvthe preparation of polychlorohydrocarbon-mxing the direct chlorination-thereof. The obvious '-,tures ,having a densityfrom' about 1.65 to about method of Vcarrying out 'the reaction. fork the 1.75 which are particularly desirable for use in r preparationof `hig'hlychlo'rinated hydrocarbonchlrinolysis reactions.l Other disadvantages of f ,y mixtures' is, of course, toirnx lthe chlorine and 15 suchvbatchwise chlorination are apparent. In-

' hydrocarbon 'compound in proportions outside sofar as we are aware,`nc satisfactory commercial the explosivelimits. This method is n ot comprocess has been devisedwhich can be operated mercially-idesirable, sinceit involves the' repeated inl continuous manner for the preparation of polyi introduction of very small proportions of'chlorine i chlorohydrocarbon vmixtures having aV specific l with'sufdvcientv time allowed lbetween each suc- 20 gravity greater than about 1.3 by the-'direct'chlov cessiveintroduction to permit reactiontooccur. r z. f Even when this'methodf'is ,'followed, vburning often results due to'higlr'local concentrations of s -i-r-'chlorine ANumerous,otherfways of carrying out yfthe reaction `have been suggested, such as causing the chlorine and hydrocarbon to react inexfv tremely narrow reaction chambers in close con- Itacttvith cooled surfaces to provide efficient cool`- 'ling of the reacting mixture, diluting the reactants xwthfan inert gas, While mixing inthe dark and 1 i thereafter reacting the materials in inert media, andvarious f other Ways.v Generally speaking,

rination of hydrocarbons yofv the group, herein concerned.

I t is, therefore, an object of the present invention toxprovide a continuous process for the lproduction of certain polychlorohydrocarbon mixtures having a desired speciogravity above about 1.3." -An additional object is to provide a continuous process for the direct chlorination of certain hydrocarbons' to produce a poiychlorohydrocarbon mixture having a desiredfspecic v.gravity above about 1.3. A further object is to provide a continuous process for the production these processes have not proven satisfactory in chlorinated hydrocarbon mixtures, using a hydro- .carbony as the' starting material', and the highly rinating va'. lower chlorinated' hydrocarbon -obcommercial practice for the preparation.' of highly chlorinatedhydrocarbonsare prepared by chloof polychlorohydrocarbon mixtures bythe chlorination of hydrocarbons withoutdanger ofvburning or of the formation of colored reaction products. A particular object of this invention i's to provide a process wherein a high economy of chlorine utilization is accomplished." 'I

We'have now found that the chlorination of hydrocarbons can be carried out rapidly and economically, and with the production of `a'mixture of highly chlorinated hydrocarbons having a specic gravity of the-product desired, by introducing a hydrocarbon having in the molecule be- L tained by methods other than direct chlorination of` hydrocarbons, such as the yaddition of chlorine to.unsaturatedhydrocarbons;`

mln-certain instances, such/asin reactions inyolving: `the production of 'hexachloroethana -ctetrachloroethylena hexachlorobutadiene, carbon tetrachloride; and hexachlorocyclopentadiene, a

l erably ,greater` than, about 1.65, and substantially l freelofchlorinatedhydrocarbons havinga spe- Y highly chlorinated hydrocarbon isdesired having l a specic gravity greater Ythan Aabout 1.3, pref# tween three and eight carbon atoms,- inclusive, and gaseous chlorine continuously and simultaneously; and at separate points substantially removed from one another, into abody of mixed polychlorohydrocarbons, maintained yat vla temperature not to exceed. substantially above veinegravity less than about vv1.3; Such polychlorohydrocarbon mixtures havelheretofore best .-L A,been prepared bythe batch-,wisechlorination of 1 A hydrocarbons or; lower chlorinated hydrocarbons degrees centgrade, preferably while causing liquid polychlorohydrocarbonsfrom the region around the point of introduction of the' hydrocarbon to -ollovvled, by v,distillation from the product ofsub- I stancesy havingban -undesirlably lowl proportion of chlorine. -Itis;diicult in such batch-Wise-chlovnow or move away from such region into the region around the point of' introduction`of chlorine. In ythis way the hydrocarbon, which is first introduced into the moving body of polychlorohydrocarbons, becomes dispersed therein and the resulting mixture then moves into the region around the chlorine inlet where the hydrocarbon reacts rapidly and smoothly with chlorine. possible also to introduce the chlorine into a moving body of polychlorohydrocarbons to produce a dispersion thereof and then to bring this dispersion into contact with thte hydrocarbon dispersion by locating the chlorine inlet below l the hydrocarbon inlet, and, while this is not our preferred mode of operation, it is intendedy to be included within the scope of our claims.

A polychlorohydrocarbon product having the desired specific gravity is withdrawn continuously from the body of liquid polychlorohydrocarbon mixture and in this way the volume of the mixture of polychlorohydrocarbons in the reaction vessel is kept substantially constant. Hydro-4 gen chloride and, usually. a small proportion of unreacted hydrocarbon evolve from the liquid in gaseous form and may be conducted away and utilized or disposed of in any way desired.

The reaction is catalyzed by exposing the body of polychlorohydrocarbon to the action of light having a wave length from about 2000 to 5000 and particularly between about,3000 to about 4000 Catalysts other than light are not employed and are preferably excluded from the reaction zone since they tend to promote the formation of color within the body of the liquid and thus to decrease the catalytic effectiveness of the light. Under optimum conditions, the reaction appears to be substantially complete within a very short time, the actual reaction time being thought to depend largely upon the length of time required for uniformly contacting the chlorine with the hydrocarbon in the region immediately around the point of chlorine introduction.

This method isparticularly applicable to the production of polychlorohydrocarbons of a specic gravity up to about 1.78. This is important inasmuch as the product produced by our method may undergo chlorinolysis in the vapor phase at 4 elevated temperatures.

The polychlorohydrocarbon product obtained is water-white in color, has a substantially constant density, and contains only small proportions of dissolved hydrocarbon and hydrogen chloride.

The product is suitable without further treatment for use directly in applications where small proportions of these substances are not disadvantageous, such as in reactions to produce hexachloroethane, tetrachloroethylene, hexachloro butadiene, carbon tetrachloride, and hexachlorocyclopentadiene, depending upon the particular product being treated and the type of treatment used. If desired, the product may be washed with water to remove hydrogen chloride and then heated to remove traces of unreacted hydrocarbon compound and other low boiling substances which may be present.l

Although it might be expected that the process described would be applicable under ordinary `conditions to the production of polychlorohydro- 05 carbon mixtures having a density less than 1.3, this is not the case. The density of the product up to 1.3 is substantially independent of the ratio of the amount of chlorine to hydrocarbon introduced. This ratio is not especially critical. It is 7o unexpected that the density of the product produced by our process does not correspond to the density of the product which would be obtained by reacting all of the hydrocarbon with all of the chlorine introduced. Even though, at the be- 75 It is 5 gquently of the product withdrawn, changes as Dalles.

ginning of the process, the reaction vessel be loaded with a polychlorohydrocarbon mixture having a density lower than that of the product desired and chlorination started, it-is found that the density rof the liquid in the vessel, and consechlorination proceeds and eventually assumes a value always above about 1.3.

From about two to about eighteen moles of chlorine is preferably used in the process for each mole vof hydrocarbon. When less than about two moles of chlorine is used for each mole of hydrocarbon, the loss of the hydrocarbon in the form of unreacted material becomes excessive and the reaction does not proceed as smoothly as ls del sired.

When the reaction is carried out with the use oi' hydrocarbon starting material having less than six carbon atoms in the molecule and it is desired to produce a polychlorohydrocarbon mixture having a. specific gravity above about 1.80, the use of pressure is advantageous.

The temperature of the body of polychlorohydrocarbon compounds wherein the reaction is carried out is maintained not to exceed substantially above 150 degrees centigrade, inasmuch as undesired chlorinolysis of certain of the polychlorohydrocarbon compounds may be initiated, and it is preferably maintained between about 50 degrees centigrade and about 125 degrees centigrade. We have found a temperature of about 100 degrees centigrade to be particularly desirable. The temperature of the body of polychlorobutanes wherein the reaction is carried out is maintained not to exceed substantially above 90 degrees centigrade, and it is preferably maintained in the range between about degrees centigrade and about 90 degrees centigrade. and we have found a temperature of about degrees centigrade to be particularly desirable. We have found that a marked decrease in temperature results in a leveling on' of the density of the product at about 1.30 when the process is carried out at a temperature of minus 40 degrees centigrade in the case of polychloroprol There is a leveling o of the density of the product at 1.52 in the case of butane and butene when the process is carried out at zero degrees centigrade. This result is obtained independently of a constant rate of ilow of chlorine and hydrocarbon in iixed proportions which would. at temperatures more elevated, produce a material of higher gravity.

Movement of liquid within the reaction zone portion of the body of polychlorohydrocarbon compounds from the region around the hydrocaron inlet to the region around the chlorine inlet may be accomplished in any convenient manner, such as by agitation designed to cause a flow of liquid from the one region to the other without at the same time causing excessive agitation of the whole body of liquid. If desired, the hydrocarbon and chlorine inlets may be situated in a conduit immersed in the body of liquid and a current of liquid caused to flow through the conduit, first. past the hydrocarbon inlet and then past the chlorine inlet. Preferably, however, the hydrocarbon inlet is situated within the body of liquid directly below and substantially removed from the chlorine inlet. Thus, when the hydrocarbon is introduced into the liquid, the density of the mixture in the region around the hydrocarbon inlet is lowered and the liquid therein rises and moves into the region around the chlorine inlet where the maior part of the reaction occurs.

Hydrocarbon and chlorine are preferably deysource of light of the desired wave length may be used, such as conventional tubular mercury lamps.

Reference is 4made to the accompanying drawing which shows a centrally cross-sectioned viewl of a particular apparatus which may be employed in practicing the process of the present inven- `tion. An apparatus, substantially as shown herein, was successfully used in carrying out the examples herein.

The apparatus is comprised of an elongated glass chlorinator tube I which is closed at its lower end I I. The glass tube I0 is provided with an overflow pipe I2 which communicates between the chamber I3 and a collector not shown.

A stopper I4 is inserted into the open upper end of the chlorinator tube I0. A gasv exhaust pipe I5, which extends into the tube chamber I3 l through an appropriate opening in the stopper I4, is connected to a scrubber or other suitable r=covery means, not shown. The lower end ofy the gas exhaust pipe I5 is positionedabove the point Where the overflow pipe I2 engages the tube I0.

A chlorine supply pipe I6, which is connected to a source of chlorine, not shown, passes through another appropriate opening in the stopper I4 and extends down within the chamber I3 to a point near the tube bottom II. A fritted glass plate I'I is secured in conventional manner to vthe lower end of the chlorine supply pipe I6.

A hydrocarbon supply pipe I8, which is connected to a source of'hydrocarbon, not shown, is received through a suitable opening inthe chlorinator tube I0 near the' bottom II thereof.

The end of said hydrocarbon supply pipe I8 withvin the tube chamber I3 preferably carries an ,alundum thimble I9 secured thereto in any convenient manner. y

The overilow pipe, thev gas exhaust pipe, the hydrocarbon supply pipe, and the chlorine su'p- .ly pipe may be glass tubes. I

A bank of tungsten filament lamps 2l, which extend substantially the entire length of the chlorinator tube I0, is positioned around and adjacent to said tube.

' The chlorinator tube I0 is filled tothe overflow pipe I2 with a liquid. polychlorohydrocarbon 22 having a specific. gravity of substantially that which is desired in the chlorinated product to ,be produced within the above-described apparaduring'the process are conducted away from the` tube chamber I3 through the exhaust pipe IU.

Certain advantages of the invention are apparent from the following examples, which are given by way of illustration only and are not to be construed as limiting:

EXAMPLE 1.-P11oPArna In order to provide a starting body of reaction medium of the desired specific gravity, a quantity of 1,2-dich1oropropane having a speciilc gravity of 1.15 was placed in a vertical Pyrex glass column one and one-quarter inches in diameter, closed at its lower end, and having an over-dow tube located about 30 inches from the closed end. About 690 grams of 1,2-dichloropropane was required to ll the reactor tube up to the over-ilow.l

Means was provided to collect liquid from the overflow tube and to conduct evolved vapors away from the top of the tube. Propane was introduced into the body of liquid through an alundum thimble located near the bottom of the column and chlorine was introduced through a fritted glass plate located about one inch directly above the propane inlet. The rates of flow of chlorine and propane vapors were rst regulated so that two volumes of chlorine were introduced into the reactor for each volume of propane. Four 20G-watt clear glass tungsten lament lamps were placed around the lower portion of the reactor column to catalyze the reaction. The product overflowing from the column was collected in 'separate successive portions, the specific gravity of each portion determined, and the process continued until the specific gravity of successive portions Was substantially constant.

In the following Table 1 there are given the specific gravities of the portions collected, the time' at which each was collected, and the amount of product in each portion. Volumes of chlorine T he procedure just described was repeated several times using, respectively, 3, 4, 5,r and .6

' volumes of chlorine for each volume of propane.

tion from the tungsten lamps -2 I catalyzes the reaction between the hydrocarbon and the chlorine.

The polychlorohydrocarbon mixture, resulting from the reaction .and having the desired speclc gravity, is withdrawn from the tube chamber I3 through the overflow tube I2, while vapors evolved The data obtained are given in the fol'owing r'espective Tables 2.3, 4, and 5.

Table 2 Vol. Chlorine-3 Vol. Propane-1 Table 3 Vol. Chlorine-i Vol. Propane-l Weight of 'Ilic' PKvgon Sp. Gr Portion,

l lo l 1 (1.15) l g 2 2 1.247 111 1 5 1o i a 1.469 252 z 15 4 i 1&4 24s l l!) f 5 1.5'il 280 i l a5 u l 1.588 I 296v 3o l 7 g 1.001 295 i i Ih s [M l Table 4 Vol. Chlorine-5 Vol. Propane-l ....I I, Time, l lorlion l g eight ofI hrs. No. i sp. (.r. Porriqon l l g x l l o l (1,15) i I 5 1 l 1.355 79 I 18 i 2 1.577 21s I 21 l a 1.613 251 :su 4 1.540 274 42 5 l 1.552 311 54 r 1.665 295 1 57.5 7 1.672 167 66 s 1.587 385 7n 9 1.691 425 so i 1. G92 46o Table Vol. Chlorine# Vol. lropaned l w h f y l zeigt o Tllgf" Rif-2 0 Sp. Gr. i' Poll-ltllm, i i g u 4 f n.15) I 5 1 I 1.359 so 14 I 2 1.581 347 2:1 1 :1 l 1. "19 399 35 1 -1 I 1.701 587 45 5 i 1.715 479 55 u 1.727 im 67 7 1.732 594 a1 x 1.738 71o 9a 9 I 1.7.19 64o 10c 1o l 1.737 om EXAMPLE 2 P110PANE EXAMPLE 3.BUrrNa The reactor described in Example l was filled to the overow with a polychlorobutane mixture having a specic gravity of 1.628. Butene and chlorine were introduced into the reactor at the respective rates of three liters and fifteen liters per hour for more than forty hours. The product which was collected from the overow had a substantially uniform specific gravity of 1.625.

EXAMPLE 4.-BU1'AN1:

The reactor described above was filled to the overflow with a polychlorobutane mixture having a specific gravity of 1.68. Chlorine and butane were introduced into the reactor in the ratio of seven moles of chlorine per mole of butane. The temperature of the reactor was maintained at zero degrees centigrade. The density of the product after forty-live hours of operation levelled oi! at 1.52 and remained substantially constant thereafter.

Mixtures of butane and butene may be used in making polychlorobutanes in substantially the same manner as shown in the examples abovedescribed.

EXAHPLE 5.-N-PINIANB A quantity of polychloro compounds of npentane having a specific gravity of 1.57 was placed into the reactor described in Example 1. Normal-pentane and chlorine were introduced into the reactor at a ratio of 8.9 moles of chlorine to one mole of n-pentane. VThe n-pentane was rst preheated by placing a cylindrical bomb containing the n-pentane in Va water bath malntained at a temperature of 70 to 'I5 degrees centigrade. The cooling on expansion of the npentane as it passed through a needle valve necessitated application of external heat in the form of a watt light bulb to prevent condensation of n-pentane. The product which was collected from the overilow had a substantially uniform speciiic gravity of 1.61.

EXAMPLE 6.--NzoHIxAm1 A quantity of polychloro compounds of 2,2-dimethylbutane having a specic gravity of about 1.6 was placed into the reactor described in Example 1. 2,2-dimethylbutane and chlorine were introduced into the reactor at a ratio of nine moles of chlorine to one mole of the 2,2-dimethylbutane. The product which was collected from the overflow had a substantially uniform speciiic gravity of 1.73.

ExAMPLr: 'L N-HnrrAm:

The reactor described in Example 1 was filled to the overflow with polychloro compounds of n-heptane having a specific gravity of 1.5. Normal-heptane and chlorine were introduced into the reactor at a ratio of ten moles of chlorine to one mole of n-heptane. The product which was collected from the overllow had a substantially uniform specific gravity of 1.7789.

The reactor described in Example l was illled to the overflow with polychloro compounds of 2,2,3-trimethylbutane having a speciilc gravity of 1.3. 2,2,3-trimethylbutane and chlorine were introduced into the reactor at a ratio of eight moles of chlorine to one mole of 2,2,3-trimethylbutane. The product collected from the overiiow had a substantially uniform specific gravity of 1.652.

cyclopentane having a specific gravity of 1.634. Clyclopentane and chlorine were introduced into one mole of cyclopeutane.v

the reactor at a'ratio of nine moles oi chlorine to The product lwhich was collected from the overilow had a substantially uniform speciilcgravity oi' 1.668.

The product which was collected from the overilow had a substantially uniform specific gravity Our processis applicable to chlorination of the y lower partially chlorinated derivatives of the aliphatic and alicyclic hydrocarbons, and can be used in the event these are available :at advantageous prices. Our improved procedure provides a simple, convenient manner of preparing the highly chlorinated derivatives of the aliphatic and alicyclic hydrocarbons having'in the molecule between three and eight carbon atoms and containing insuicient chlorine to cause the production of material amounts of solid derivatives. A particular advantage of our process resides in the fact that mixtures of substantially uniformly highly chlorinated products are obtained ysubstantially free from lower chlorinated derivatives.

Reference is made to our copending applica tions Serial 618,788 and 618,789, both filed September 26, 1945, the former now abandoned. in which are described a continuous process for the chlorination of butane 'I to produce a highly chlorinated polychlorobutane mixture and a continuous process for the chlorination of propane to produce a highly chlorinated polychloropropane mixture, respectively. In the said applications the stated subject matteris more particularly described and speciically claimed.

We claim:

1. The method which includes: (l) maintaining a body of liquid polychlorohydrocarbons (A.) having the same number of carbon atoms in the molecule as the starting material (B) and a specic gravity greater than the starting material (B), said speciilc gravity of (A) being greater than about 1.3; (2) continuously introducing,

through diusion means into said liquid body (A) at a point in a first region thereof, a starting material (B) selected from the group consisting of .aliphatic and alicylic hydrocarbons and partially chlorinated aliphatic and alicyclic hydrocarbons, having in the molecule between three and eight carbon atoms, inclusive, said starting material (B) having a specific gravity less than that of the body of liquid polychlorohydrocarbons (A) into which said starting material (B) is introduced; (3) introducing chlorine into a second region of said liquid body (A) (4) causing liquid polychlorohydrocarbon (A) containing dispersed starting material (B) to move continuously from the one region into the other regionin the liquid body (A) (5) catalyzing the chlorination reaction with actinic light; (6) maintaining a temperature between about zero degrees and about 150 degrees centigrade in the reaction zone; (7) maintaining a chlorine to starting material (B) mole ratio between about 2 to 1 and 18 to l; and,

r(8) continuously withdrawing a liquid poly- .chlorohydrocarbon product (C) having a substantially constant specific gravity greater than about 1.3 and greater than that of said starting material (B) from an upper portion of the said 'body of liquid (A) at a point removed from saidiirst and second regions.

' 2. The process as claimed in claim 1, wherein the amount of chlorine introduced is between about 2 and about '10 moles for each mole of starting material (B) introduced.

3. The process as claimed in claim 1, wherein the temperature ofthe reaction zone is maintained between about 50 degrees and about 125 degrees centigrade. f

4. The process as claimed in claim 1, wherein the starting material (B) contains at least four carbon atoms in the molecule, and wherein the specc gravity of the polychlorohydrocarbon product (C) is greater than about 1.5.

5. The method which includes: (1) maintaining a body of liquid polychlorobutanes (A) having a. speciilc gravity greater than the starting material (B), said specic gravity of (A) being greater than about 1.52; (2) continuously introducing through diffusion means into said liquid body (A) at a point in a irst region thereof, a starting material (B) consisting of butanes, said starting material (B) having a speciilc gravity less than about 1.52 and less than that of the' body of liquid polychlorobutanes (A) into which said starting material (B) is introduced; (3) introducing chlorine into a. second region of said liquid body (A): (4) causing liquid polychlorobutanes (A) containing dispersed starting material from the one region to move continuously into the other region in the liquid body (A): (5) catalyzing the chlorination reaction with actinic light; (6) maintaining a temperature between about zero degrees and about 9 0 degrees centigrade in the reaction zone; (7) maintaining a chlorine to starting material (B) molar ratio of about 7 to 1 and suilicient to convert the (B) introduced to a product (C) of the desired specic gravity; and (8) continuously withdrawing a liquid polychlorobutane product (C) having a substantially constant specific gravity greater than about 1.52 and greater than that of the said starting material (B) from an upper portion of the said body of liquid (A) at a point removed from the said rst and second regions.

6. The process as claimed in claim 5, wherein the body of liquid polychlorobutanes (A) has la speciic gravity greater than about 1.6; and wherein the liquid poiychlorobutane product (C) has a substantially constant specic gravity greater than about 1.6.

7. The process as claimed in claim 5, wherein the body of liquid polychlorobutanes (A) has a specic gravity greater than about 1.6 wherein the liquid polychlorobutane product (C) has a substantially constant specific gravity greater than about 1.6; and wherein the reaction mixture is maintained at a pressure greater than atmospheric.

8. The process as claimed in claim 5, wherein the temperature of the reaction Vzone is maintained between about '10 and about 90 degrees centigrade.

9. The method which includes: (1) maintaining a body oi liquid polychlorobutanes (A) having a specic gravity greater than the starting material (B), said specific gravity of (A) being greater than about 1.52; (2) continuously introducing through diffusion means into said liquid starting material (B) having a specic gravity` starting material (B) molar ratio of about to 1 and sulcient to convert the (B) introduced to a product (C) of the desired specific gravity; and (8) continuously withdrawing a liquid polychlorobutane product (C) having a substantially constant specific gravity greater than about 1.52 and greater than that of the said starting material (B) from an upper portion oi the said body `oi liquid (A) at a point removed from the said rst and second regions.

10. The process as claimed in claim 9, wherein the body of liquid polychlorobutanes (A) has a specific gravity greater than about 1.6; and wherein the liquid polychlorobutane product (C) has a substantially constant speciilc gravity greater than about 1.6.

11. The process as claimed in claim 9, wherein the body of liquid polychlorobutanes (A) has a speciiic gravity greater than about 1.6; wherein the liquid polychlorobutane product (C) has a substantially constant speciilc gravity greater than about 1.6; and wherein the reaction mixture is maintained at a pressure greater than atmospheric.

l2. The process as claimed in claim 9, wherein the temperature of the reaction zone is maintained between about 70 and about 90 degrees centigrade.

13. The method which includes: (1) maintaining a body of liquid polychloroneohexanes (A) having a speciilc gravity greater than the starting material (B) said specific gravity of (A) 12 being greater than about 1.6; (2) continuously introducing through diimsion means into said liquid body (A) at a point in a Ilrst region thereof. a starting material (B) consisting ot neohexane, said starting material (B) having a specic gravity less than about 1.6 and less than that oi the body ot liquid polychloroneohexanes (A) into which said starting material (B) is introduced; (3) introducing chlorine into a second region of said liquid body (A): (4) causing liquid polychloroneohexanes (A) containing dispersed starting material from the one region to move continuously into the other region in the liquid body (A): (5) catlyzing the chlorination reaction with actinic light; (6) maintaining a temperature between about degrees centlgrade and about degrees centigrade in the reaction zone; (7) maintaining a chlorine to starting material (B) molar ratio of about 9 to 1; and (8) continuously withdrawing a liquid polychloroneohexane product (C) having a substantially constant speciilc gravity greater than about 1.6 and greater than that of the said starting matarial (B) from an upper portion of the said body of liquid (A) at a point removed from the said first and second regions. A

EARL T. McBEE. LAWRENCE W. DEVANEY.

REFERENCES CITED The following references are of record in the ille of this patent:

UNITED STATES PATENTS Number Name Date 1,191,916 Brooks et al. July 18, 1916 1,248,065 Blanc Nov. 27, 1917 1,523,563 Snelling Jan. 20, 1925 2,015,044 Teichman et al. Sept. 17, 1935 2,147,577 Hass et al. Feb. 14, 1939 2,193,824 Lockwood et ai. Mar. 19, 1940 2,200,255 Bender May 14, 1940 2,368,495 Schiller Jan. 30, 1945 2,377,669 Brown et al. June 5, 1945 

